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OF
AQUEOUS SULFIDE-SULFITE-THIOSULFATESYSTEM
Tung Siu
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Tung Siu
Abstract
been performed. A simplified reaction scheme has been proposed to describe the system,
and the investigation stratedes were set up accordingly. The reaction between sulfide
and thiosulfate was studied at pH 5 - 7, and its rate equation was found to be
~ S 2 0 ~ ' - ] /=
d t~&O>]W~S]. Thiosulfate formation by reaction between sulfide and
k B [ ~ ~ ] [ ~ ~ Mechanisms
0i]'. for the above two reactions have been postulated. ther
reactions of sulfide and sulfite were treated as a single reaction and its rate equation was
model was established to predict the system behavior at pH 7. The experimental data
agreed with the model prediction in a satisfactory manner, indicating the same reaction
Dr. Charles Q. Jia for his invaluable scientific advice, exceptional patience, and
The author would also like to extend his appreciation to al1 the members in this
iii
Table o f Contents
..
Abstract Il
...
Acknowledgements 111
List of Tables vi
I. Introduction 1
2. Literature Survey 4
3. Expenmental Section
3.1 Chernicals
3.3 Apparatus
Nomenclatures
References
Appendices
Appendix C. Calculations
Table
12. Reaction Orders With Respect to Sulfide and Sulfite for Reaction
(34).
Figure
9. Plot according to equation (23) with data obtained for reaction (2a)
at pH = 6.00, T = 20 O C , I = 0.10 M with total sulfide concentration
of 1.21 mM.
1o. Plot according to equation (24) using kinetic data of reaction (2a) at
pH = 6.00,1= 0.10 M, and T = 20 O C with total sulfide concentration
of 1.21 rnM.
Il. Plot according to equation (14) for reaction (2a) at pH = 6.00 and T
= 20 O C .
vii
15. Eyring plotofln (k'7) vs. VTforreaction(2a). 51
produces sulfuric acid (H2S04) and leads to the "acid rain", which has been proven to
have adverse effects on aquatic and forest life. As well, acid rain harms the urban
Damage due to acid deposition in Canada is mainly caused by sulfur dioxide emissions
Rom smelters and fossil-fuelled power plants in eastem Canada and from power plants in
the midwestem and northem United States (Milbum-Hopwood and Puckett, 1992).
In 1985, the Canadian sulfur dioxide control program was established, whereby
the seven eastem provinces agreed to achieve, by 1994, a 50 percent reduction in annual
sulfr dioxide emissions fiom the 1980 base value of 4.5 million tonnes. In 1990, the
federal and provincial environment ministen agreed to expand the program to al1 of
Canada and pemanently cap sulfr dioxide emissions at 3.2 million tonnes by the year
reduced national SO emissions by 43% fiom 1980 levels to 2.65 million tonnes. In
eastem Canada, SOI emissions were d o m by 54% fiom 1980 levels to 1.7 million tonnes
As a result of the legislation of sultiir dioxide emission, a large number of flue gas
those put into commercial practice. The rnost widely applied FGD technique, for coal
fired power plants which normally have less than 1% sulfur dioxide in the off gases, is
(CaS04*2Ht0)is obtained. Such FGD facilities were first installed in the early 1970s in
Japan and the US, followed by a major expansion in Europe during the late 1980s (van
Velzen, 1991). Nowadays, a substantial part of FGD gypsum is used for the production
of wallboard.
For smelters who produce off gases with very high levels of SO2 (10 - 80?),
sulfuric acid, liquid sulfir dioxide, and elemental sulfbr are the more common FGD
products (INCO,1989). The disadvantages of both sulfwic acid and liquid S 0 2 products
are their high storage and transportation costs. According to a 1989 marketing report
(INCO, 1989), the net backs of sulfuric acid and liquid S02 are a loss of C$2O/tome and
storage and transportation problems (the net back, shown by the same marketing report,
is C$65/tome) and thus a more attractive FGD by-product, especially for smelters at
process (Henderson, 1973), carbon in Foster Wheeler "RESOX" process (Bischoff and
Steiner, 1975), hydrogen sulfide in Claus process (INCO Ltd., 1990) and Citrate process
(INCO Ltd., 1985), carbon monoxide (Hibbert and Campbell, 1988), and metal sulfide
(Strong et al., 1974; Talonen and Poijarvi, 1990; Olper and Maccagni, 1996).
directly produces elemental sulfbr; (2) reduces the number of steps and of the necessary
equipment units; (3) is easily operated and controlled, with low operating costs; and (4)
does not produce any substance that may require further processing in order to be
found that the simultaneous S02 absorption and elemental sulfr production is feasible at
observations (see Section 2.1) in this study, a fully understanding of the system would be
advantageous for funher promotion of elemental sulfbr conversion. However, the lack of
results of this study will not only provide usehl information for further development of
this SP-FGDprocess but also contribute to the knowledge of inorganic sulfbr chemistry.
The up-to-date kinetic infonnation from this work may also find its application in other
The terms sulfide and sulfite hereinaf'ter used include protonated and anhydrous
fonns, Le. S" + HS' + H2Sand S O ~ "+ HSOi + SOI, unless otherwise specified.
aqueous NazS solution at high temperature (90 OC), was developed in 1993 and patented
in 1996 (lia, 1993; Jia and Lu, 1996). The main product of this process is H2Sgas, which
is then fed into a Claus plant to react with SOI and generate elemental sulfur. The
simplified flow sheet of this proceu is shown in Figure 1. The use of a Claus plant,
however, could limit the applicability of this process because of its high capital cost.
the Claus unit, in the above system was conducted in this group (Liu et al., 1998). It was
found that the simuitaneous Sot absorption and elemental sulfur production is feasible at
lower temperatures (O - 40 OC). Two types of reactions namely acid-base reactions and
redox reactions, occur in this &S(aq)-S02(g) system. The acid-base reactions are
necessary for providing a favorable pH environment for redox reactions that lead to
elemental sulfur formation. On the other hand, the acid-base reactions also compete with
redox reactions for sulfide by hydrolyzing S" and H S ions to produce HIS,which will
escape to the gaseous phase. Some important observations of this study include:
similar to that observed at high temperatures (Jia and Lu, 1996). A great
portion (> 99%) of elemental sulfur is produced in the second stage where the
(2) The amount of elemental sulfur fonned increases with decreasing temperature
(3) The relative recovery of elemental sulfur decreases with increased initial Na2S
concentration.
Based on this study, the authors proposed a new SP-FGDflow sheet. The new process,
generation unit, sulfur dioxide is absorbed into sodium sulfide solution and convetted to
elemental sulfur via redox reactions at low temperatures. After separating sulfur fiom the
spent iiquor and drying, sodium sulfite/thiosulfate in solid fonn is reduced to sulfide in
the reductive burning reactor (RBR)where coke or carbon is partially bumed to provide
heat and gaseous reductants. The tapped sulfide fiom RBR is then dissolved in water and
It is expected that the new flow sheet, by eliminating the Claus unit, would lower
the capital and operation costs of the SP-FGD process. However, there are several
obstacles, such as the low conversion efficiency of S 0 2 to s0(s) and the significant
emission of H2S even at O O C , in the way of realizing this new process. The observations
Figure 2. pH changes and elemental sulfur formed at different stages. Na2S: 0.025 M;
SOI: 1CF%; temperature: O f 1 .O OC; feeding gas: 200 ml/min. (afier Liu et al., 1998)
I
Figure 3. Proposed new SP-FGD process. RBR = Reductive Burning Reactor. (fier
Liu et al., 1998)
2.2 Osidation-Reductioa Reactions in Sulfide-Sulfite System
The reactions between H2S and S02 in gaseous phase (Peter and Woy, 1969) or
organic solvents (Diah et al., 1972;Neumann and Lynn, 1986; Hix and Lynn, 1991) lead
This is the well-known "Claus Reaction". It was shown by Neumann and Lynn (1986)
that the reaction in organic solvent is first order with respect to both reaaants. Hix and
Lynn (1991) showed that the catalytic (by 3-pyridylcarbinol) reaction in poly(glyco1
H2S and SO2, the pH dependence of redox potentials, and other factors. Riesenfeld and
Feld (1921)and von Deines and Grassrnann (1934) studied the aqueous reaction of H2S
and S 0 2 with H2S presented in suficient excess and found that elemental sulfur is
forrned almost exclusively. The elemental sulfr formation from this reaction was later
studied by Heijde and Aten (1953) using "S labeled H2Sand S02. These authors found
that elemental sulfr originates fkom H2S and SO2 in the ratio of 2: 1.
thiosulfate (Kundo et al., 1987; Pai and Kundo, 1989), the latter being a stable product in
In the neutral to weak alkaline solution, reaction of sultite and sulfide leads to
thiosulfate formation. Foerster and Mommsen (1924) and Urban (1975) reported that the
reaction produces thiosulfate almost predominantiy. This reaction was studied by Neiman
et al. (1952) and Barbieri and Majorca (1960) using "S labeled H2S. It was found that
two thirds of thiosulfate formed was radioactive. Both groups proposed the same
mechanism in which elernental sulfur is first formed and consequently reacts with sulfite
to produce thiosulfate:
2 ~ 2 +~SO?
s + 2H20+ 2% +S (3)
temperature.
Reaction (4) is the so-called "sulfite degradation" of elemental sulfur and its
detailed stepwise mechanism was provided by Schmidt and Siebert (1973). The reversal
of this reaction is the decomposition of thiosulfate, which occurs at low pH (< 3), where
the sulfur chain is built up stepwise followed by a ring closure via an intramolecular &2
form hydrogen sulfide and sulfr trioxide (Schmidt and Siebert, 1973):
The Wackenroder's liquid (Blasius and Burmeister, 1959; Stamm et al., 1960), a
mixture of hydrogen sulfide and excess sulfr dioxide in aqueous solution, is perhaps one
(HSxOs, x = 3-6) were found fiom this mixture. These polythionic acids are stable only
give thiosulfate, sulfate, sulfite, elemental sultr, and lower polythionates through the
~ ~ 0 + 6s0j2-
~ -_) ~ ~ 1 0 6+~ ' (8)
There is no experimentally secured mechanism for the formation of polythionic acids and
elemental sulfur. Generally it is believed that S-S bonds formation and elongation are
Foerster and Janitzki (193 1) studied the action of "sulhrous acid" upon metallic
(Fe, Mn, and Zn) sulfides by passing SOI into a suspension of the sulfides in water. It
was found that at the early stage of the reaction thiosulfate and fiee sulfur are largely
fonned. With the frther course of the reaction polphionates are formed with gradua1
suppression of thiosulfate. The authors concluded that the polythionates formation is a
result of reaction between thiosulfate and sulfite and is favorable at low pH's. The
studies by other researchers (Muller and Mehlhom, 1934; Janickis, 1935) showed that
these phenornena also occur in other sulfide-sulfite systems. Battaglia and Miller (1968)
showed that the reaction of sulfite and thiosulfate at pH 3.60 to 4.10 results in the
formation of trithionate:
4HSOf + s203'-+ 2w + 2 ~ ~ 0 6+ ~3H20
- (9)
The sulfoxylic acid intennediate was proposed originally by Bassett and Dunant (1924)
The products in this redox system are complicated and very much dependent on
the pH of the solution and the ratio of the two reactants (sulfide and sulfite) as well. At
moderate to high pH's (27) and when sulfide is the limiting reagent, thiosulfate is the
prevailing product. In acidic solutions with sulfide present in suficient excess, elemental
sulfr is formed predominantly. When surplus sulfite is available at acidic pH's, al1 three
products, i.e., elemental su1fur, thiosulfate, and polythionates can be found in the system.
thiosulfate system is obvious. Teder and Wilhelmsson (1975) studied the reaction
phase concentration of HIS,the authon observed two parallel reactions in the reacting
system, a very rapid autocatalytic reaction and a slower one. The rapid reaction occurs
only when sulfide is mixed into a sulfite solution. The slower reaction, which is
independent of how the reactants are mixed, was found to be approximately first order
with respect to both sulfide and sultite, with a "rate constant" in the order of 105 M's".
The activation energy of the slow reaction was determined to be only 2 k.i/mol. The
authors attributed this extremely low activation energy to the combination of the low
''real" activation energy and the effect of temperature on the equilibria involved.
Nonetheless, these authors' use of gaseous HIS concentration changes to represent the
aqueous chemical reaction rate is quite questionable, since the interfacial mass transfer of
In an earlier study, Kundo et al. (1987) showed that the reduction of thiosulfate by
hydrogen sulfide (reaction 2) was more than 100 times slower than that of sulfite at pH
5.0, in terms of the disappearance of H2S in gaseous phase. Since thiosulfate formation
was identified in the reaction of sulfite and hydrogen sulfide, the authon used silicon
oxide and aluminum oxide to catalyze the reaction between thiosulfate and hydrogen
sulfide in order to increase elemental sulfur yield. The catalysts were found to be able to
A systematic kinetic study of this catalytic reaction was later conducted by the
same group (Pai and Kundo, 1989). The gaseous phase concentration of H2S was
w =I ( I S 2 0 3 2-1
15
[H2s]n[r]m ( 1 1)
calculated from gaseous H2Scontent, assuming instant interfacial equilibrium (again, this
is questionable). When the partial pressure of H2S,Ptus > 0.02 MPa, n = 0.2 and when
Pms < 0.02 ma,n = 1; m = 1 at pH < 5.0 and m = O at pH > 5.0. Under reaction
conditions of PHts > 0.02 MPa, pH < 5.0, and T = 40 - 70 OC, the activation energy and
frequency factor were reponed as 62 kJlmol and 83.3 M1 7s-1, respectively. While the
'
typical fiequency factor values for aqueous bimolecular reactions have the order of
is indeed dubious.
Battaglia and Miller (1968) in the pH interval from 3.60 to 4.10. The temperature jump
(chilling of the reacting solutions) technique was used to "stop" the reaction at
appropriate mes and the concentrations of both reactants were detemined by iodometric
with averaged k value of 2.2 x 106 Mds*'. A detailed mechanism was postulated as
follows:
s ( o ~ ( s ~ o J+~SIO:
~' + S ~ O ?+ 20K + S 2 0 3 (9e) slow
2.4.2 Sdl/iie
Sulfite can be detemined in water by titration with iodine (Kolthoff and Belcher,
1947), cesium(1V) (Bruno et al., 1979), or mercury(I1) (Dryssen and Wedborg, 1986).
determination of low levels (0-25 mgk) of sulfite in water. The method involves the
Ion chromatography (IC) has been applied to determine sulfite in the presence of
arsenate (Hansen et al., 1979), sulfate and thiosulfate (Sunden et al., 1983), halide and
nitrite (Oikawa and Saitoh, 1982), dithionite (Petne et al., 1993), and phosphate (Oikawa
and Saitoh, 1982; Stevens and Turkelson, 1977). Marko et al. (1984) reported a gradient
and Saitoh, 1982) showed that the NalCOdNaH eluent is more suitable than
~ 0 ,by~IC-,however, was found to be unreliable mainly due to (1) the oxidation of SO~"
' O2 in the eluent Stream (Hansen et al., 1979), and (2) the poor separation of
to S O ~by
2.4.2 ~ i o s u l f P f e
thiosulfate (Konig, 1985). The method is selective for thiosulfate in the presence of
hydrogen sulfide, sulfite, polysulfides and elemental sulfur. Reproducible results were
2.4.3 Suifide
do not interfere.
Sulfide has also been determined in natural water by potentiometric titration with
blue method, Grasshoff and Chau, 1971), sodium nitroprusside (Bethea and Bethea,
Al1 these methods are capable of detecting wlfide at 10 mg/L (ppm) levels with
Works on sulfide ion-selective electrodes (ISEs) have been reported by Hseu and
Rechnitz (1968), Sekerka and Lechner (1977), and Radic and Mark (1985). The
Intefierences are mainly fkom cyanides and halides (Light and Swartz, 1968). Teder and
Wilhelmsson (1975) reponed erroneous results given by a sulfide ISE in the reaction
(Williams, 1985). It is convened into hydrogen sulfide in the suppressor column while
the latter is a weak acid that does not ionize sufficiently to be detected with a
conductivity detector.
2.4.4 Surfore
Various titration procedures have been described for the detemination of sulfate.
These include reaction with excess barium ions and back titration of unconsumed barium
with EDTA (McKellar et al., 1978), direct titration with barium ions (Basargin and
Nagina, 1969), and direct titration with lead ions (Archer, 1957).
Jasinski and Trachtenberg (1973) described an indirect method using femc ion-
selective electrode. Excess femc ions were added to complex sulfate. The solution was
then titrated with barium chloride and the liberated ferric ions were detected with the
femc ISE. Parts per million levels of sulfate could be determined with a precision of
c3%.
Singh et ai. (1991) determined sulfate in deep sub surface waters using suppressed
3.1 Chemicals
The chemicals listed below were comrnercially available fiom the suppliers
indicated. Unless otherwise noted, al1 were reagent grade and were used as received
BDH,Inc.
Hydrochloric Acid, 36.5 - 38.0%
Iodine, 99.8%
Al1 the solutions were prepared with deionized-distilled water, which was
deaerated by bubbling through nitrogen gas for about 30 minutes just before using.
in an oven for one hour and cwled to room temperature in a desiccator. A weighed
was then standardized by iodometric titration with potassium iodate standard solution
using starch indicator (Kolthoff and Belcher, 1947). The sodium thiosulfate solutions are
Iodine. This solution was prepared by dissolving a weighed sample of iodate free
KI and 12 in cold water. The solution was standardized by iodometric titration using the
above standardized thiosulfate solution (Kolthoff and Belcher, 1947).
titration (Kolthoff and Belcher, 1947). The concentration of this stock solution was
determined to be 2.4 12(2) M. The stock solution was kept in an airtight bottle to prevent
being oxidized by oxygen in air. Fresh solutions for kinetic studies were prepared just
before use by diluting the stock solution to desired concentrations with deaerated buffer
solutions.
solution was standardized with standard iodine solution. According to Raschig (1904),
accurate results are obtained only when the sulfite solution is used as titrant and added
directly fiom a burette into a measured amount of standard iodine solution until the latter
by weight agreed with that determined by titration (0.2% difference). However, even
when deaerated water is used, the solution is subject to oxidation by oxygen in air. An
4.5% decrease in concentration in 8 hours and 11% decrease in 24 hours were observed
by titration and sulfate was detected in this solution by ion chromatography. The fresh
sulfite solutions for kinetic studies were prepared just before use and the concentrations
weighed sample of K&P04 was dissolved in an appropnate volume of water to give the
stock solution of O. 100 or 0.200 M.
used to dilute stock Na2S solution or to prepare sodium thiosulfate and sodium sulfite
solutions.
Zinc Chloride. A 0.05 M ZnC12 solution was prepared by weighing out a sample
14.28 g NaHCO3 (NO DRMNG!) in 1 L boiled and deaerated water. Fresh solutions for
ion chromatography elution were prepared just before using by diluting the stock solution
100-fold.
3.3 Apparatus
In the first two stages of the experiments, a 250 rnL single-neck round bottom
glass flask was used as the reactor for aqueous reactions conducted. The reactor was
Inc.). The reacting system was closed to prevent emission of H2S and oxidation of HzS
anNor sulfite by air. in the last part of the experiments, a set of 15 test tubes (1 10 x 16
mm) was used in place of the above reactor for reaction times under 300 seconds.
3.4 Experimental Procedures and Analytical Methods
In the first stage of experiments, reactions between thiosulfate and sulfide were
conducted in the above-mentioned flask reactor. Two volumetric flasks each containing
100 mL NazS solution or 100 mL Na2SIOi solution were kept in water bath at reacting
temperature for 30 to 60 minutes until thermal equilibrium was achieved. The solutions
of the two reactants were then mixed into the reactor. During the course of reaction, 5.0
mL aliquots of the reacting solution were pippetted fkom the reactor at vanous times and
injected immediately into test tubes containing 1.O0 mL or more 0.05 M ZnC12 solutions
to precipitate sulfide. When reactions were conducted at high pH's (7 - 1 1), aliquots of
1.00 rnL 0.01 M HCI solution were mixed with each of the ZnC12 solutions to prevent
solutions, had pH around 6. Under these conditions, the concentrations of free sulfide
ions in the solutions were calculated as below 10"' M and reaction between sultide and
thiosulfate was considered to be stopped. These solutions were then filtered using
syringe filter units with 0.22 Fm pore sire polytetrafluoroethylene (PTFE) membrane.
In the second stage of experiments, reactions between sulfide and sulfite were
studied at pH 8 - 9 using the same flask reactor. The sampling procedures were similar
to that of the first stage. Following IC analyses of thiosulfate, a certain volume (1 .O0 to
5.00 mL) of the sample was pipetted into a 50 rnL volumetric flask; treated with excess
iodine solution to oxidize sulfite to sulfate; and diluted to the mark. The sulfate
The test tube reactors were used in the third stage to study reactions between
sulfide and sulfite at pH 7. The reactant solutions and the empty test tubes were first kept
in the water bath for thermal equilibrium. Aliquots of 2.50 rnL of each reactant were then
mixed into the test tube. At 20 to 300 seconds after mixing, 1.O0 rnL ZnCl2 solution was
added into the reacting solution to precipitate sulfide. The resulting samples were treated
the same way as in the fira and second stages. For reacting time longer than 300 seconds
thiosulfate and sulfate concentrations. The IC was equipped with a GD40 gradient pump,
lonPac@AS4A-SC colurnn (4 x 50 mm) was used to separate thiosulfate and sulfate ions
eluent with constant flow rate was used. The suppressor levei was set at 50 mA and the
processor. The interface between the instrument and the computer was achieved by using
v. 4.5 1 software package provided by Varian was used to collect and analyze the data.
The pH values were measured using an Orion 520A pH meter with automatic
thiosulfate calibration curve was obtained using six standard sodium thiosulfate solutions
with concentrations ranged fiom 3.79 pM to 190 pM. For each concentration, three
replicates were injected. A linear response curve was obtained as shown in Figure 4.
The dope and the correlation coefficient (R') were calculated, using least-square linear
For sulfate measurement, the calibration curve was obtained in the concentration
range of 56.3 pM to 704 pM. The dope was calculated to be 1.1 l(2) x 10'' counts/pM
and the comelation coefficient f? was calculated to be 0.9973. The calibration curve is
shown in Figure 5.
For thiosulfate, the six-sample RSD, using a standard solution with concentration of
92.06 pM, was detemined to be 0.7?6(92.1 2 0.6 m. The six-sample RSD for sulfate
main, source of error in the kinetic study of the reaction For a chemical reaction with
translated into a k7 - 13% change in the rate constant, when the reaction is conducted
Peak Area,
6
1o6counts
this work was carried out by an RTE-8 circulating water bath, which is capable of
A single sampling procedure in this work, as described in Section 3.4, would take
3 - 5 seconds. For the slower reactions where the sampling intervals are longer than 5
minutes, the uncertainties in time measurement are insignificant (less than 1%). Greater
errors of 3 - 8 % occur when the sampling intervals are 1 to 2 min. In the third stage
experiment, when the reactions were studied within the first 100 seconds, the large
time measurement.
In this work, the concentrations were determined by (1) volumetric titration, (2)
calculation fiorn weight of the sample and volume of the solution, and (3) ion
chromatography (IC). The error associated with IC has been discussed above. Each
volumetric titration was repeated three times and the relative standard deviations were in
the range of 0.2 - 0.5%. The balance (Acculabe V-lmg t o m Labequip Ltd.) used in this
work has the accuracy of 0.001 g. Al1 the samples weighed out were more than 0.2g and
Volume measurernents were carried out using pipettes and volumetric flasks. No
calibration has been made to the volumetric flasks and the levels of accuracy claimed by
solutions, a micro-pipette (Finnpipette om Labsystems, 200 - 1000 pL) has been used.
The calibration of this pipette at its 1.000 mL level (by transfemng 12 aliquots and
weighing them) showed a relative standard deviation (RSD) of 0.3%(1 -001 t 0.003 mL).
Similar calibrations have been conducted for other pipettes. For the 5, 10, and 25 rnL
In al1 cases, the kinetic measurements have been repeated at least three times.
Averaged results are reported in this thesis in the format of 'k.xx(x)" where the number
in the parenthesis represents the standard deviation at the last digit of the averaged value.
4. Results and Discussion
reaction scheme has been proposed at the beginning of current investigation. The
behavior. In the reaction scheme, pathway A represents al1 possible reactions leading to
elemental sulfur without formation of thiosulfate. This pathway also includes, although
not show in the scheme for simplicity, other reactions between sulfite and sulfide such
intermediate.
Based on the scheme and the preceding studies in this group (Liu et al., 1998), the
(1) The pH range has been confined from 5 to 9, corresponding to the "second
stage7' in the study of Liu et al. (1998), where a great portion of elemental
(2) Reaction C, i.e. reaction between sulfide and thiosulfate, has been studied
sulfide and the analytical dificulty of sulfide, the pseudoorder technique has
been employed where the total sulfide concentration has been kept in large
(3) Reactions between sulfide and sulfite have been studied at pH 8 - 9, while
by this reaction. The initial rates of the reactions have been measured in
(4) By combining the kinetic data obtained in step (2) and (3), a theoreticai
model has been established to predict the system behavior at lower pH's
conducted and the results have been cornpared to the model prediction.
dk
r = - d [ ~ t ~ , " ] l= t WzS]" mb
~ ~ 2 0 3 ~ 7 (13)
in which the rate constant k and the reaction orders a, b, and c are to be detennined.
constant dunng the course of reaction. The reactant ~203' is therefore isolate and a
where A" = km2S]oa. By expenmentally following [s20?], the reaction order c and
The reaction order o can be obtained by either (1) setting [LO~"]~>> [H2SIoand
studying the pseudo-ath-order kinetics with respect to H2S;or (2) using various m2S]o to
obtain different k" values and calculating a and A'. The second method was used in this
detennine the reaction order with respect to W, b, and the rate constant k, according to
of the reacting solution. The reacting system was closed during the course of reaction
except for sampling and therefore the loss of H2S fiom gaseous phase is considered to be
negligible. Under the condition of pH 5 - 7, [s"] cm be ignored and the aqueous H2S
where K Iis the first acidic dissociation constant of H2S. The dimensionless correction
represents the gaseous panition of sulfide. and are the average gaseous and
aqueous volumes (in L) of the reacting system; H (in Umol) is the Henry's law constant
of H2S, which is calculated fiom H2S solubility data (Lange's, 1985); R is the gas
constant (in J/mol-K) and T is the absolute temperature. The g values at different
temperatures are listed in Table 1. The highest fiaction of H2S in gas phase is calculated
to be 13% under experimental conditions. Since the total sulfide concentration was kept
at least IO-fold in excess over thiosulfate, the pseudo-order condition was maintained in
aqueous phase.
For al1 the kinetic experiments conducted, the total sodium sulfide concentrations
as mentioned before.
The fractional time method introduced by Wilkinson (1961) was used to
Table 1. Gaseous Phase Pmition Constants (g)for Sulfide at Various Ternperatures.
Temperature, O C g
determine the reaction order 4 t h respect to thiosulfate based on eq (13"). For simplicity,
let [s~Q'-]
= x and [S~O?'I~
= xo, the integrated form of eq (1 39, for c # 1 is
-
Define the fiaction reacted, p = 1 x/xo and substitute into eq (19), it gives
The same equation can be obtained for c = 1. A plot of t/p vs. r leads to an estimate of the
order c fiom the slope. Since eq (23) was denved by means of approximations, erron
may ocau in the estimation. Connors (1990) reported that for first-order reactions, using
eq (23) would slightly overestimate the order, giving c values of 1.2 - 1.3. Eq (23) also
applies to higher p values (Connors, 1990), although the assumption of small p was used
The experimental data are tabulated in Appendix A and example data sets are
shown in Figures 7 and 8. One set of kinetk data obtained at pH 6.00 and T = 20 O C is
plotted according to eq (23) in Figure 9. The slope was calculated to be 0.53 and thus c =
O 1O0 200 300 400
Time, min.
Figure 7. Expermental data obtained for reaction (2a) at pH = 6.00,1= 0.10 M, and T =
20 O C with total suldde concentration of 1.21 rnM (circles) and 12.1 rnM (triangles).
O 20 40 60 80 1O0 120
Time, min.
550
500
t,,p,min. 450
400
350
300
Figure 9. Plot according to equation (23) with data obtained for reaction (2a) at pH =
6.00, T = 20 O C , 1 = 0.10 M with total sulfide concentration of 1.21 mM. The slope ( d 2 )
is calculated to be 0.53.
1.06. Data obtained under different pHs (5 - 7) and sulfide concentrations were also
analyzed in the same way and the reaction order c was found to be 1.04 - 1.11,
obtained. The plot of the sarne data set mentioned above is shown in Figure 10. The rate
constant k" and linear correlation coefficient # were calculated as 4.54(7) x IO'.' s" and
The reaction order with respect to H2S was obtained using eq (14). Hydrogen
mentioned in Section 4.2.1. The plot according to eq ( 14) for reactions at pH = 6.00 and
into account the experimental errors, it can be concluded that the reaction is first-order
with respect to hydrogen sulfide. Therefore the rate constants k' were calculated by using
the relation k" = kv2S]o, i.e. by plotting k" vs. [HISIO. The plot for pH 6.00 is shown in
Figure 12 and the calculated k' values at various pH's are listed in Table 3.
It is obvious from Table 3, that the rate constants k' fluctuate only slightly over a
one-hundred-fold hydrogen ion concentration range (pH = 5 - 7). This leads to the
conclusion that the reaction is zeroth-order with respect to W, Le. b = O. The rate
constant k at 20 OC was thus calculated as the averaged k' value, i.e. k = 0.045(1) MIS-'.
O 100 200 300 400
t ,min.
Figure 10. Plot according to equation (24) using kinetic data of reaction (2a) at pH =
6.00,I = 0.10 M, and T = 20 O C with total sulfide concentration of 1.21 rnM. The rate
constant k" is calculated to be 4.54(7) x s". (x = [S~O~'-Jand x . = [~203'-]0)
Table 2. Pseudo-First-Order Rate Constants k" for Reaction (2a). ( T = 20 OC and Ionic
Strength O.1O M)
" The averaged values of three measurements are reported. The numbers in parentheses
represent the standard deviations at the last digits ofk" values.
Figure 11. Plot according to equation (14) for reaction (2a) at pH = 6.00 and T = 20 O C .
The reaction order a (the dope) is calculated to be 0.98. The error bars represent one
standard deviations.
Figure 12. Plot of the pseudo-fistader rate constant, k", as a fnction of hydrogen
sulfide concentration for reaction (2a) at pH = 6.00,1= 0.10 M, and T = 20 OC. The rate
constant k' is calculated to be 0.0454(9) M's-! The error ban represent one standard
deviations.
Table 3. Calculated Second-Order Rate Constants, k, for Reaction (2a) at Various pH.
(lonic Strength 0.10 M and T = 20 O C )
4.2-3 Rea~n'onsConduced <ir Higker pH's
change in thiosulfate concentrations over a period of 8 hours (see Appendix A-6). This
The redox potential of reaction (2a) can be calculated using the Nernst equation.
Zhdanov, 1985)
Substituting the highest thiosulfate and total sulfide concentrations used in this study
(0.001 M and 0.01 M, respectively), it can be s h o w that a pH value lower than 7.6 is
the activation parameters. Experimental data are compiled in Appendix A and sample
data sets are plotted in Figure 13. The calculated rate constants k were obtained as listed
Figure 13. Experimental data obtained for reaction (2a) at pH = 6.00,1= O. 10 M and
different temperatures with total sulfide concentration of 6.03 mM. Circles: T = O O C .
Squares: T = 20 OC.
Table 4. Calculated Second-Order Rate Constants for Reaction (2a) at Different
Temperatures. (pH = 6.00 and Ionic Strength 0.10 M)
lnk=lnA-EJRT (26)
-
ln (WZ) = ln (k$h) + MIR M I R T (27)
where ke is Boltzmann constant and h is Planck's constant. The activation parameten are
mechanism in the rate-detemining step (Schlaeger and Long, 1963), where two reactant
molecules are converted to a single transition state particle, with a loss of disorder of the
system.
reacting solutions affected the reaction rate only slightly, as shown in Table 6. The
experimental data are listed in Appendix A-8. For bimolecular reaction, the relationship
between rate constant and ionic strength can be expressed as (Laidler, 1987):
where 4 and ZBare charges of the reactants, A is the Debye-Huckel constant, and ko is
the rate constant extrapolated to zero ionic strength. The plot of log k against 2M1" Qives
a dope ZAZBof 0.09. which suggests that a neutral molecule is involved in the rate-
detemining step of the reaction (Laidler, 1987). The deviation of ZAZBfiom zero can be
attributed to the simplification in eq (28), where the limiting Debye-Huckel law is used.
A mechanism that is consistent with the observed rate law and stoichiometry of
where eq (29) is rate detennining. Multiplying eqs (29) to (32) by 2 and adding up the
reacting solution was made in this work but it failed to demonarate the existence of any
intermediate because of the high absorption of sulfide and thiosulfate in the UV region.
A related intermediate ~ 4 0 ' ' was proposed by Licht and Davis (1997) in their study of
distinguish it from the rate constants of pathways A and B in the reaction scheme.
Based on the reaction scheme, the reactions between sulfide and sulfite diverge in
Reaction (5) is the pathway B in the reaction scheme with its stoichiometry mggeaed by
Heunisch (1977). Reaction (34) is the pathway A in the scheme that represents al1 other
reaction between sulfide and sulfite leading to produa(s) 'F' which may include
Q = d[S~~~]lcir
=k H ~ ~ - ] " ~ ~ ~ i(35)] b ~
and " '[HI]' '
r~ = -d[HSO,']ldt = ~ [ H S J '[Hso~] (36)
The sulfite consumption rate for reaction (S), a ' = -d[HS03ldi, can be related to the
thiosulfate formation rate by the stoichiometry of reaction (5) as m ' = (413)m. The total
~~=~y-f~'=--(4/3)~ (37)
Thiosulfate formation and sulfite consumption were followed to determine the rate of
dope of the curve gives the initial rate of the reaction. The rate equation at t = O is
written as
Thus by measuring ro at various values of CAh the log-log plot yields the reaction order.
This method also works if the rate equation includes the concentrations of other reactants,
provided their concentrations are held constant throughout the series of measurement
(Connors, 1990). Casado et al. (1986) have analyzed the error of estimating the initial
rate fiom a tangent to the concentration-time curve at r = O. Their result shows that the
enor is kept well within the accepted limits for kinetic studies (+100/0) if the extent of
In the current kinetic study of reaction between sulfide and sulfite, the initial rate
method was applied. The measurement of sulfite concentrations was used as a means of
monitoring the extent of the reaction and thus the total concentrations of sulfite were
always kept lower than or comparable with that of sulfide. In one rare case the reaction
was allowed to proceed to 13% (in ternis of decrease in sulfite concentration) to ensure
that suficient data were obtained. The concentration-time curves were subject to the
conventional linear least-square regression and the slopes fkom the regression were taken
M, and temperature T = 20 OC. The expenmental data are tabulated in Appendix B the
thiosulfate concentrations as a ftnction of time are plotted in Figures 16 - 17. The initial
concentration the reaction was repeated three times and the averaged values of initial
rates are reported in Table 7 together with the standard deviation. The orders with
The a and b values at various pH's along with the standard deviations and correlation
Figure 16. Experimental data obtained for reaction (5) at pH 9.0% I = 0.20M, T = 20 OC
with total sulfide concentration of 2.41 m M and dHerent total sulfite concentrations of
0.793 m M (circles), 1.08 mM (squares), and 2.38 m M (triangles).
O IO 20 30 40 50 60 70
Tirne, min.
Figure 17. Experimental data obtained for reaction (5) at pH 9.00, I = 0.20 M, T = 20 O C
with total sulfite concentration of 2.38 m .and dif5erent total sulfide concentrations o f
2.4 1 rnM (circles), 6.03 rnM (squares), and 9.65 m M (tnangies).
Table 7. initial Rates of Thiosulfate Formation r~ and Calculated Rate Constants k~ ' at
Various Sulfide (CNaIs)and Sulfite (CNaI~03)Concentrations. (1= 0.20 M and T = 20 OC)
coefficients (d),
are show in Table 8.
It is evident fiom Table 8 that the reaction is first order with respect to sulfide and
second order with respect to sulfite. The rate constant ks ' = kB[H'Ic can therefore be
ks ' = ~BWST'
WSO<]-~ (39)
The HS' and HS0; concentrations are calculated fiom the total concentrations in the
same way as mentioned in Section 4.2.1. The calculated rate constants k~ ' are listed in
Table 7. The average kB' values at pH 8, 8.5, and 9 are 3.6(2), 4.1(2), and 3.7(1)( x 1o3
M-2s"), respectively. The log ks ' vs. pH plot gave a slope of 0.008(ka' = k e [ ~ ' ] ~ + ~ ~ ) .
Thus, the rate constants k~ ' can be considered as pH independent and k~ = k~ '. The
The calculated rate constants are listed in Table 9 and the activation parameters fiom
Arrhenius plot (eq 26) and Eyring plot (eq 27) are listed in Table 10. The negative
The ionic strength effect was studied in the range of0.20 to 1.0 M, at pH = 9.00,
and T = 20 OC. The rate constants at ionic strength of 0.20, 0.50, and 1.0 M are
determined to be 3.8(3) x l d , 11.2(6) x IO', and 37.1(7) x Io3 bf2s-', respectively. The
plot according to eq (28) gives a dope ZAZBof 1.8,which indicates that two charged
Based on the kinetic data, the following mechanism is proposed for the reaction of
Table 8. Reaction Orden With Respect to Sulfide (a) and Sulfite (6)in Thiosulfate
Formation. (I = 0.20 M and T = 20 OC)
Table 9. Calculated Rate Constants of Reaction (5) at Different Temperatures.
Tabk 10. Activation Parameters of Reaction ( 5 ) at pH = 9.00 and Ionic Strength 0.20M.
t hiosulfate formation:
2 ~ ~ 0 3 '0,s-Sa-
~ - (9 + H20 (40) fast, Kl = kl/k-l
'03S-SO< + H S + ~ 2 0 3+
~ HSOi
- (II) (4 1) slow, k2
The intermediate (n)is the deprotonated fom of sulfoxylic acid, which was proposed by
Bassett and Durrant (1924). Compound (1) has been known by a nurnber of names
including metabisulfite and pyrosulfite. The name disulfite is more appropriate than the
others since the X-ray crystallography showed the molecule contains no S-O-S bridge
(Lindquist and Morsell, 1957). Reaction (40) was studied by Betts and Voss (1970), who
reported kl and kei values of 700 MIS-' and 104 s-', respectively. I f the steady-state
approximation is applied to both intermediates (1) and (II), the thiosulfate formation can
The assumption of k.1 k@S] will re-generate the observeci rate law where >Cg =
2Klkt. Thus RI can be calculated, using kB detemined above and KI from Betts and Voss
(1970), to be 2.6 x 10' MIS? Under the current experimental conditions, [HS7 is in the
18 shows the detailed mechanism of this step. An empirical comlation has been found,
by Davis et al. (1966), between the activation energy of such a displacement reaction and
1S
Il
-0-S-0-
Il
O
(Thiosulfate)
where rss is the sulfur-sulhr bond length (in Angstroms) and C is a constant
characteristic of the neucleophile. For HS' the C value is 130 kcalmol" (Ciuffarin and
Pryor, 1963). Using S-S bond length of 0.221 nm in disulfite (Lindquist and Morsell,
1957), the activation energy for reaction (41) is calculated to be 50.3 IcJrnol-', which
The sulfite concentrations were also monitored by IC foi lowing the procedures
It was found that the overall rate of sulfite consumption is always higher than that
calculated fiom stoichiometry of reaction (4). One example is illustrated in Figure 19.
This observation suggests that pathway A in the reaction scheme exists although the
product(s) of the reaction(s) is unidentified. The whole pathway A was treated as a single
reaction (34) and its kinetics was studied in a similar way as the thiosulfate formation.
The initial rates r.4 of sulfite disappearance for reaction (34) were calculated as
per eq (37) and are listed in Table 11. The reaction orders with respect to sulfide (a 3 and
sulfite (b ') were determined using eq (38') and are tabulated in Table 12. While the a '
values are quite consistent, the order of HSOf is actually pH dependable, ranging from
1.4 to 1.7. The averaged value of b ', i.e. 1.5, was chosen and the rate constants k.4 ' =
kAmC'
are calculated according to:
The averaged kA' values at different pH's are listed in Table 13. The plot of log k ~ vs.
'
O 20 40 60 80
Ti,min
Figure 19. Sulfite concentrations as a function of time in reaction between sulfide and
sulfite at pH = 9.00,1= 0.20 M, and T = 20 OC. Circles: expenmental data with c N . 2 ~=
2.4 1 m M and Cwso3 = 2.38 mM. The solid line represents the calculated sulfite
consurnption rate based on stoichiometric relation of reaction (5).
Table I l . Initial Rates of Reaction (34) r.4 at Various Sulfide and Sulfite Concentrations.
(Ionic Strength 0.20 M and T = 20 OC)
Table 12. Reaction Orders With Respect to Sulfide (a')and Sulfite (b') for Reaction
(34).(Ionic Strength 0.20 M and T = 20 OC)
Tabk 13. Rate Constants k~ ' of Reaction (34) at Various pH. (Ionie Strength 0.20 M
and T = 20 O C )
- pH gives a c ' value of - 0.6(1). The average k is calculated to be 5(1) x 10" P 6 s - ' .
By combining the kinetic information obtained in Sections 4.2 and 4.3, the
equations:
t ~B[HS] [ H S O ~ -
4 ~ 2 0 P y d= ] ~~ W S[ S] Z O ~ ~ ~ (46)
calculated f?om the mass balance. An alternative way is to use a sufficient excess of
sulfide experimentally so that the ternis WS]and [H2S] in the above equations are
Using the test tube reactors and following the procedure descnbed in the
and T = 20 OC with total sodium sulfide concentration of 0.0121 M and initial sodium
sulfite concentration of 7.94 x 104 M. Equations (46) and (47) are now converted into:
dCniJdt = 8 . 7 ( ~ ~ -&2.7
~ x) 1~o4 Cmio (46')
2
= 12(c~&so3)+ o.0 1 l ( ~ ~ ~ ~ 3 ) ' (47')
-dCNr2soddt ''
where Cm,, and C N d ~ 3are thiosulfate and sulfite concentrations, respectively. The
predicted curves of Cnio and C N are ~shown ~ 20 and 21, dong with the
~ in Figures
~
experimental data.
sulfite in reaction 34) and c' (order of H' in reaction 34). The details are given in
Appendix D. The two most sensitive parameters are identified to be k~ and kc. The
effects of f10V0 changes in these two parameters are show by the contour lines in
Figures 20 and 21. It cm be seen that most of the data poims are included in this 10%
lower pH's. The large experimental errors (10 - 15%) at the beginning of the reaction are
attributed to the relative uncertainties in time measurement during the first 100 seconds
of the reaction.
O 200 400 600 800 1O00 1200 1400
time, s
Figure 20. Theoretical prediction according to equation (46') (middle solid line) and
experimental data (a) of thiosulfate concentrations in reaction of sulfide and sulfite at pH
7.00, ionic strength 0.20 M, and T = 20 OC. The upper and lower contour lines show a
k1OO/o change in ke and kc.
O 300 600 900 1200 1500
time, s
Figure 21. Theoretical predidon according to equation (47') (middle solid line) and
experimental data (*) of sulfite concentrations in reaction of sulfide and sulfite at pH
7.00, ionic strength 0.20 M, and T = 20 O C . The upper and lower contour lines show a
k1 % change in ks.
5. Summrry o f Main Findiogs and Environmental Implication
-d[s20a/dt = k c ~ 2][S~O>~-]
s (48)
stoichiometry equation (2a) and the rate equation (48) has been postulated in the
following sequence:
The reaction (2a) has also been conducted at pH 8 to 1 1 and no significant change in the
The reaction between sulfide and sulfite is very complicated and the products
depends on pH and the ratio of the two reactants (see Section 2.2.4). The kinetics of
75
thiosulfate formation
has been studied at pH 8 to 9 where reaction (2a) does not interfere. The rate equation of
2 ~ ~ 0o3 '03S-Soi
~ - (1) + H20 (40) fast, Ki = k ~ / k - ~
-03S-SOi+ H S + ~ 2 0 3 +~ HSO;
- (II) (4 1) slow, kt
By applying steady-state approximation to both intermediates (1) and (II), and assuming
k.1 >> k2mS], the rate equation (49) is regenerated in which ke = Xlk2 (see Section
4.3.2 and Appendix C-4 for details). The activation energy determined for reaction (5)
also coincides with the calculated value using an empirical correlation by Davis et al.
(1 966).
It was found, in reaction between sulfide and sulfite, the rate of sulfite
describe the system behaviot. The experimental data obtained at pH 7 agree with the
of our new SP-FGD process, as mentioned in Sections 1.2 and 2.1. The aqueous
chemistry of the second stage (see Figure 2) in Sot absorption, where pH ranges fiom 5
The pH and temperature effects on the thiosulfate behavior are very imponant in
the process development. Table 14 shows the pH effect on reactions (2a) and ( 9 ,
assuming constant total sulfide and sulfite concentrations. It can be seen that when pH
2 while that of thiosulfate formation decreases by 53%. This implies that a lower pH in
the range of 5 to 9 is beneficial for the improvement of elemental sulfr conversion (fiom
thiosulfate). Temperature also has different effects on the two reactions because of their
different activation energies. The relative reaction rates of reactions (2a) and (5) at
various temperatures are listed in Table 15. It shows that higher temperatures are
A rather contiising phenornenon obwrved in the previous study in this group (Liu
et al., 1998) is that the relative recovery of elemental sulfr decreases with increasing
in sulfide concentration will increase the rate of pathway A by 5 times and that of
pathway B by 10 times. Since pathway A eventually l a d s to elemental sulfur formation
depressed.
The findings of this study also have their potential application in other air
pollution control processes, e.g., H2Semission control, where sulfide andior sulfite are
involved.
Tabk 14. pH Effects on Relative Reaction Rate of Reactions (2a) and (5).
1.8 O .43
2.0 0.47
Tabk 15. Temperature Effect on Relative Reaction Rates of Reactions (2a) and (5).
9.2 4.2
62 15
6. Conclusions and Recommendations
been perfonned. To the author's knowledge the kinetic data reported and the
mechanisms proposed in this work are unprecedented and are of impofiance in both
inorganic sulfur chernistry and industrial applications. The proposed reaction scheme
(Figure 6) and mathematical mode1 (equations 46 and 47), although greatly simplified,
The results also show that in neutral to weak basic solutions, thiosulfate is fonned
(Foerster and Janitzki, 193 1; Muller and Mehlhom, 1934; Strong et al., 1975; Talonen
and Poijawi, 1990). The analysis of pH and temperature effects on reactions (2a) and (5)
shows that lower pH's and higher temperatures are beneficial for the thiosulfate
transfa of H2S fiom aqueous solution to the gas phase, which is to be avoided. This
conflict introduces a potential problem in our SP-FGD process development and the
search and study of catalysts for reaction (2a) will be mandatory in the ttture.
Owing to the lack of reliable analytical method for sulfide, its time-dependence
has not been studie in the cumnt investigation and fiinire work on this subject wodd be
of great interest. Other kinetic studies that should be pursued in the tiiture include (1)
system behavior et lower pH's (< 7), and (2) polysulfides and polythionates formation.
Nomenclature
reaction orders
frequency factor
reaction orders
reaction orders
total concentration of x, M
redox potential, V
activation energy, k~rnol'~
gaseous phase correction terni defined in eq. 18
Henry's law constant, J ~ O T '
enthalpy of activation, kJmol"
ionic strength, M
ion chromatography
rate constants
arnount of x, mol
fraction reacted
reaction rates, MS"
rss sulfur-sulfirbond length, Angstroms
R gas constant, ~ r n o l - ~ ~ '
R' correlation coefficient
RSD relative standard deviation
As entropy of activation, mol"^'
time, s
temperature, O C or K
volume, rnL
charge of ion x
References
Bartlett, P. D.; Davis, R. E.; Cose, E. F. J. Am. Chem. Sm. 1%1,83, 1 03.
Bhat, S. R.; Ecken, J. M.; Geyer, R.; Gibson, N. A. Ana%Chim. Acta 1980, 114,293.
Bruno, P.; Caselli, M.; DiFano, A.; Trahi, A. Anal Chim. Acta 1979, 104, 379.
Hansen, L. D.; Richter, B. E.; Rollins, D. K.; Lamb,J. D.; Eatough, J. Anal. Chern. 1979,
51(6), 633.
Pane, L. M.; Jakely, M. E.; Brandwig, R L.; Kroenings, J. O. A m 1 Chem. 11993, 65(7),
952.
Strong, H. W.; Radway, J. E.; Cook, H. A. Cyclical Prucess for Recovery of Elemental
S~@wfromWme Guses;U . S . Patent 3,784,680, January 8, 1974.
Sunden, T.; Lingrom, M.; Cedergren, A.; Siemer, D. D. Anal Chem. 1983,55(1), 2.
van Velzen, D. St@r Dioxide and Nimgen xides in Indusha1 Wuste Gases:
Emission, Legislaiion, and A bateme~tt,van Velzen, D. Ed. ; Kluwer Academic
Publishers: Netherlands, 1991.
kGs
= 1.21 mM. Dilution Factor = 1.2
ks
= 2.4 1 mM. Dilution Factor = 1.2
T h e (min) Cs203 (M
repeat 1 repeat 2 repeat 3
-------------------------
- - - - P b ------
O 79.3 77.9 78.4
1O 77.2 75.1
15 75.8
20 73.9
$0 68.3
50
60 67.8
65
80 62.4
90
100 60.4
120 56.0
135
150 54.2
160
180 47.5
190
200
220
240 43.8
250
300 33.6
340
350
360 31.0
MO
T h e (min.) Cs203 (m
-------- weat 1 w t 2 repeat 3
-- ----
-
O 78.7 78.6 79.5
2 75.5 76.3 76.9
5 70.3 73 .O 73.9
8 66.6 68.5 68.5
12 62.1 63.6
15 56.9 58.5 59.2
20 55.1 53.2 55.0
25 44.7 45.5 51.7
30 41.7 41.7 47.5
35 37.8 37.7 41.1
40 35.0 35.3 35.8
kS
= 12.1 mM. Dilution Factor = 1.4
Time (min.)
repeat 1
Cs03 (m
repeat 2 repeat 3
&= 1.2 1 mM Dilution Factor = 1.2
Time (min.) Cs03 (CrM)
repeat 1 repeat 2 repet 3
-- -----
----------------- -----
- - 3 - - - - - - -
kS
= 2.4 1 mU Dilution Factor = 3
= 6.03 mM. Dilution Factor = 2
-----------------
--------------- repeat 1
-----A
------repeat
tepeat2
-------
-- 3
O 145 148 149
5 139 141 144
10 131 137 139
15 123 132 134
20 116 127 129
30 111 117 119
JO 100 108 110
50 97.1 101 103
60 92.7 94.0 96.4
70 88.7
80 82.6 81.3 82.7
100 66.3 69.7 71.0
Time (min)
CNCs= 12.1 mM. Dilution Factor = 1.6
Time m.)
A-7. Temperature ERect, pH = 6.00,I= 0.10 M.
Time (min)
T h e (min.) Cs203 (m
------- -Pd---
m-
i1-----
re~eat2 repeat 3 ----
---------
O 78.0 72.5 75.1
1O 74.1 70.8
20 71.2 66.6 72.8
10 65.1 62.8 67.8
60 58.3 57.0 60.9
80 53.1 5 1.4
90 50.7
100 47.4 45.4
120 42.9 41.8 38.9
110 37.3
150 37.4 34.4
160 33.4
180 32.3 30.0 30.6
200 26.3
2 10 27.2 26.5
240 23.6 23.1
300 18.0
Appendix B. Esperimental Data of Reactions Between Sulfide and Sulfite.
1 . Experimental data:
Time (min.)
2. Calculate lnCdC, where Cois the initial thiosulfate concentration and Cris the
concentration at time t.
t (min.)
3. Use linear least-square regression method to fit the above data into the Iinear relation
of tnC& = k"t. The LINEST worksheet fiinction in Microsoft Excela was used.
4. The average value ofk" is calculated to be 4.8(1) x 10'' S-' and reported in the main
text (Table 53rd column, 6th row).
C-2. Sample calculation for initial rates and rate constants of reactions (5) and (34).
1. Expenmental data:
2. Use linear least-square regression method to detemine the initiai rate, i.e., plot C vs. f
and calculate the dopes. The LINEST function in Microsofi Excel@was used.
repeat 1:
average:
r, = 9.50(8) x 10" W ~ S - ~ =.
= 1.79(8)x 10" M'S.'. 'R = 0.99 19.
. 0.9758.
r~ = r~ - (4/3)rB= 7.1 1 x IO-' W'S-'.
Alnk = ( E J R ~AT
)
d[~z05"]ldt = R I W S O ~-]~
~ ~ [ s I-o~?z ]
~sIo?]~s]
d[HSOf]ldt = I[S~O~S[HS] - QWSOi]
Applying steady-state approximation, i.e., setting the above rates to zero, the following
equations can be reached:
(iii)
3. &25% change in kc (only CThio - t plot is show since sulfite is not affected by kc):
Time, s 1